Cd-Doped Polyoxotitanium Nanoclusters with a Modifiable Organic Shell for Photoelectrochemical Water Splitting

Yi-Xin Wu; Xue-Ru Liu; Guo Chen; Yi-Qi Tian; Jun Yan; Xiao-Yi Yi; Chao Liu

doi:10.1021/acs.inorgchem.1c03078

Cd-Doped Polyoxotitanium Nanoclusters with a Modifiable Organic Shell for Photoelectrochemical Water Splitting

Inorg Chem. 2021 Dec 20;60(24):19263-19269. doi: 10.1021/acs.inorgchem.1c03078. Epub 2021 Nov 24.

Authors

Yi-Xin Wu^{1

2}, Xue-Ru Liu³, Guo Chen¹, Yi-Qi Tian¹, Jun Yan¹, Xiao-Yi Yi¹, Chao Liu¹

Affiliations

¹ Hunan Provincial Key Laboratory of Chemical Power Sources, College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, P. R. China.
² College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. China.
³ College of Chemistry and Materials Science, Northwest University, Xi'an 710127, P. R. China.

PMID: 34817992
DOI: 10.1021/acs.inorgchem.1c03078

Abstract

Incorporating heterometal and chromogenic groups into the titanium oxo cluster (TOC) nanomaterials is one of the effective strategies for the development of new high-performance photoelectrically active materials. In this Article, we report the structures and photoelectrochemical (PEC) performances of a family of TOCs, including pure [Ti₁₂O₈(OEt)₁₆L₈] ({Me-Ti₁₂}) and six Cd-doped clusters formulated as [H₄Cd₂Ti₁₀O₈(OEt)₁₆(L)₈(H₂O)₂] ({Cd₂Ti₁₀}; L = salicylic acid and their derivatives). The six Cd-doped clusters are isostructural, containing the same {Cd₂Ti₁₀O₈} core, but are protected by salicylic ligands modified with different functional groups. The compositions, structures, and solution stability of these clusters have been studied in detail by single-crystal X-ray diffraction and electrospray ionization mass spectrometry measurements. The embedding of heterometallic Cd(II) and chemical modification of organic protective shells can effectively regulate the PEC water oxidation activity of those clusters, with {F-Cd₂Ti₁₀} having the highest turnover number of 518.55 and the highest turnover frequency of 172.85 h^-1. Our work highlights the potential of using TOCs that do not contain noble metals as water oxidation catalysts, and their catalytic activity can be regulated by structural modification.